This invention relates to a process for preparing 1-nitroanthraquinone substantially free of dinitroanthraquinone.
In the processes hitherto known for producing 1-nitroanthraquinone from anthraquinone and nitric acid, nitration and purification of the resulting 1-nitroanthraquinone have proved very difficult.
Either the products obtained are not pure enough for conversion into dye intermediate products or the yield of pure product is so low as to render the process uneconomical. Thus, for example German Offenlegungsschrift No. 2,162,538 claims the nitration of anthraquinone in nitric acid with a mole ratio of at least 20, in particular from 24 to 50. (The term "mole ratio" is used herein to denote the ratio of nitric acid to anthraquinone or anthraquinone plus nitration products.)
The reaction is stopped by the addition of considerable quantities of water, with the result that the product obtained is purified by the dilute nitric acid thereby formed. The substances which go into solution, apart from a small quantity of 1-nitroanthraquinone, are mainly 2-nitroanthraquinone, anthraquinone and 1,6- and 1,7-dinitroanthraquinone. Approximately 92% pure 1-nitroanthraquinone has been obtained by this method in a maximum yield of 74.5%. (All percentages herein are by weight unless otherwise stated.)
Since the dilute nitric acid formed must be worked up and in some cases regenerated, it is a serious economic disadvantage to have to stop the reaction with a large quantity of water. For this reason, German Offenlegungsschrift No. 2,227,340 claims so-called nitration inhibitors, such as nitrites, phosphates or phosphoric acid, which are intended to reduce the reaction velocity. The disadvantage of this method is that it introduces foreign substances into the reaction mixture so that a separate operation is required to work up the nitric acid.
Another possibility for stopping the nitration of anthraquinone with excess nitric acid has been described in German Offenlegungsschrift No. 2,220,377.
To regulate (reduce) the reaction velocity, the process described uses nitric acid diluted only to such a degree that, at the end of the nitration reaction, the total nitric acid content of the mixture is still above the azeotropic limit (68% nitric acid). Whereas nitric acid which has a concentration of at least 93%, and preferably 97%, is used for nitration and a mole ratio of from 20 to 120 is employed, the nitric acid used to reduce the nitration velocity is preferably at a concentration of from 70 to 80%, so that when nitration is terminated the nitric acid content of the nitration mixture is preferably from 75 to 90%.
The resulting reaction mixture is separated into nitration products and two nitric acid fractions. If desired, the crystallised nitration product may first be separated and the remaining nitric acid fractionated, or alternatively a highly concentrated nitric acid may first be removed from the reaction mixture and the remaining mixture may then be divided into nitration product and dilute acid. The concentrated nitric acid should then be used again for subsequent nitration reactions and the dilute nitric acid for regulating the reaction velocity.
The relatively large quantities of dilute nitric acid obtained by this operation result in a purer 1-nitroanthraquinone obtained by nitration because the major portion of the reaction by-products and the unreacted anthraquinone (with the exception of 1,5- and 1,8-dinitroanthraquinone) are dissolved in the dilute nitric acid while the 1-nitroanthraquinone crystallises. The disadvantages of this process lie in the fact that complete or partial purification of this dilute acid is necessary if the acid is to be used again to stop the reaction and hence act as a purifying agent to obtain a reasonably pure 1-nitroanthraquinone.
The quantities of nitric acid which have to be handled are enormous. If, for example, nitration is carried out with a mole ratio of about 38 to 40:1 and the reaction is stopped with 74-78.5% nitric acid, then the mole ratio after stopping the reaction is 78 to 100:1 (the proportion by weight of the resulting 78 to 87% nitric acid to anthraquinone plus nitroanthraquinone derivatives being approximately 22 to 37:1 ).
In spite of these enormous efforts, the 1-nitroanthraquinone obtained is at the most 91% pure and the yield is approximately 65%. The product still contains substantial quantities of anthraquinone, 1,5-dinitroanthraquinone and 1,8-dinitroanthraquinone and cannot be used directly for the production of dye intermediate products without further purification.
Thus, for example, German Offenlegungsschrift No. 2,206,960 describes the treatment of partly purified products which contain dinitroanthraquinone with aqueous Na.sub.2 SO.sub.3 solution in the presence of sodium hydroxide solution. The 1-nitroanthraquinone obtained by this method also has a maximum purity of only 97% (the remainder consisting of 1,5- and 1,8-dinitroanthraquinone). In addition to 2-nitroanthraquinone and part of the dinitroanthraquinones, about 5% of 1-nitroanthraquinone enter the aqueous filtrate in the form of intensively coloured water-soluble compounds, and, together with the inorganic sulphur compounds, they heavily contaminate the effluent water.
Other methods for completely separating the by-products of nitration, e.g., washing with acid amides (German Offenlegungschrift No. 2,039,822) or treatment with saturated chlorinated hydrocarbons which contain nitric acid (German Offenlegungsschrift No. 2,142,100) result in 1-nitroanthraquinone which is only 95-96% pure (with a total yield via nitration and purification of 42 to 43%).
No process has hitherto been described by means of which a very pure 1-nitroanthraquinone, almost free from dinitroanthraquinone, can be obtained in economical yields.
It has now surprisingly been found that very pure 1-nitroanthraquinone, which is almost free from dinitroanthraquinone and which can be used directly for the preparation of dye intermediate products, can be prepared without producing large quantities of dilute nitric acid, with the result that the nitration process can be rendered much more economical and much time, energy and expenditure of apparatus can be saved. In this process, anthraquinone or a mixture which contains anthraquinone is nitrated in the presence of highly concentrated nitric acid, in particular in &gt;90% nitric acid, with a mole ratio of nitric acid to anthraquinone of &lt;20:1 and at a temperature of .gtoreq.0.degree. C, in particular .gtoreq.45.degree. C; and the reaction is stopped by cooling the reaction mixture to temperatures below 30.degree. C and/or by lowering the mole fraction of nitric acid e.g., by the addition of diluents such as water and/or by distilling off nitric acid; the 1-nitroanthraquinone is precipitated, either by further cooling of the reaction mixture and/or by further reducting of the mole fraction of nitric acid, e.g., by the addition of diluents such as water and/or dilute nitric acid, in particular &lt;90% nitric acid and/or by further removal of nitric acid by distillation; and the precipitate is isolated and freed from nitric acid, in particular by vacuum drying, and finally subjected to vacuum rectification.
In the text which follows, the term "mole fraction" is used herein to denote the mole fraction of nitric acid in a given total mixture in accordance with the following equation: EQU .gamma..sub.HNO.sbsb.3 = n.sub.HNO.sbsb.3 /(n.sub.HNO.sbsb.3 + n.sub.N + n.sub.H.sbsb.2O)
where
n = number of moles, and PA1 N = nitroanthraquinone derivatives and anthraquinone.
The process according to the invention is characterised in that anthraquinone or a mixture which contains anthraquinone is nitrated with at least 90%, and in particular 95-100%, nitric acid at temperatures of at least 0.degree. C, in particular .gtoreq.45.degree. C, preferably 55.degree.-75.degree. C, and with a mole ratio of nitric acid to anthraquinone of &lt;20:1, in particular 6:1 to 15:1; the reaction is stopped when the anthraquinone conversion is .gtoreq.50%, in particular 80 to 100%, by cooling the reaction mixture to temperatures .ltoreq.30.degree. C and/or by adjusting the mole fraction of nitric acid to a value .ltoreq.0.86, for example by the addition of water and/or removal of nitric acid by distillation; 1-nitroanthraquinone is thereafter precipitated by adjusting the mole fraction of nitric acid to a value of from 0.7 to 0.4 by distilling off nitric acid and/or by diluting with water and/or by adding dilute nitric acid, and/or the 1-nitroanthraquinone is precipitated by lowering the temperature to .ltoreq.20.degree. C; and the precipitated 1-nitroanthraquinone is separated off and subjected to vacuum distillation, optionally in the presence of solvents which are stable under the conditions of distillation, which are inert towards nitroanthraquinone and which boil at temperatures between 100.degree. and 350.degree. C.
By mixtures which contain anthraquinone are meant mixtures which, in addition to anthraquinone, contain nitroderivatives of anthraquinone such as 1-nitroanthraquinone, 2-nitroanthraquinone and di-nitroanthraquinone.
The relative proportion of anthraquinone to nitro-compounds of anthraquinone in such mixtures is not critical for the process according to the invention, but mixtures containing at least 50% by weight of anthraquinone are normally used.
The process of nitration according to the invention can be carried out in conventional reaction apparatus such as flow tubes, tank cascades or separate tanks, either continuously or discontinuously. In order to obtain maximum possible yields of 1-nitroanthraquinone in continuous processes, the flow, if flow tubes are used, should be a distinct plug flow and Reynolds numbers should be .gtoreq.2300; if cascades or tanks are used, an ideal spectrum of residence times in the apparatus should be achieved. The reaction is preferably carried out adiabatically or partly adiabatically but may, of course, also be carried out isothermally.
When nitration is carried out with mole ratios of nitric acid to anthraquinone of from 6:1 to 19:1, for example using 99% nitric acid, mole fractions of .gamma..sub.HNO.sbsb.3 = 0.69 to 0.87 become established. The point at which the reaction is stopped depends on the mole fraction of nitric acid in the mixture and of course also on the temperature. The reaction mixture must be adjusted to lower mole fractions at higher temperatures than at low temperatures.
If, for example, nitration is carried out with a mole ratio of 19:1, 15:1, 10:1 or 6:1, the reaction may be stopped by cooling to temperatures of .ltoreq.-5.degree. C, .ltoreq.5.degree. C, .ltoreq.15.degree. C or .ltoreq.30.degree. C respectively. The corresponding mole fractions are .gamma..sub.HNO.sbsb.3 = 0.871; 0.847; 0.793 or 0.694. The appropriate mole fractions may, of course, also obtained by stopping the reaction by rapidly distilling off concentrated nitric acid. At higher temperatures, the reaction mixture, must, of course, be adjusted to lower mole fractions. Thus, for example, at 65.degree. C (45.degree. C, 25.degree. C) and mole ratios of 18:1, 10:1 and 5:1, the appropriate acid concentrations are about 86% (90; 93), 91.5% (93.5; 95.5) and 95.5% (96.5; 97.5) and the appropriate mole fractions are 0.615 (0.692; 0.758); 0.702 (0.744; 0.791) and 0.733 (0.754; 0.775). These values can easily be obtained if water is added to the reaction mixture to stop the reaction.
In the same way as the stopping of the reactions, the purification by crystallisation is also dependent upon the temperature and the mole fraction of nitric acid in the nitration mixture. Since nitric acid has a relatively high vapour pressure at elevated temperature, it would appear more suitable to filter off the crystallisate at room temperature or temperatures of up to 30.degree. C. The quantities and concentrations of nitric acid required for purification depend upon which impurities are to be separated and in what quantities. If, for example, 10% by weight (5% by weight) of anthraquinone is to be removed from the nitroanthraquinone mixture, then the acid concentrations may be adjusted, for example, to about 93% (82%), 84% (78%), 80% (76%) or 76% (72%) and the mole fractions accordingly to .gamma..sub.HNO.sbsb.3 = 0.69 (0.53), 0.58 (0.49), 0.52 (0.47) or 0.46 (0.42).
The same applies, of course, to the separation of 2-nitroanthraquinone from nitroanthraquinone mixtures. If, for example, about 8% by weight of 2-nitroanthraquinone and less than 3% by weight of anthraquinone are to be separated, then the mole fractions must be adjusted to .gamma..sub.HNO.sbsb.3 = 0.51; 0.49; 0.47 or 0.42 if the acid concentrations are about 80%, 78%, 76% or 72%. In order to keep the loss of 1-nitroanthraquinone by separation as small as possible, the mole fractions should be large (small), i.e., the mole ratios small (large), when the acid concentrations are high (low).
The larger the quantity of appropriately diluted nitric acid, the smaller is the loss of 1-nitroanthraquinone by separation, but large quantities of dilute nitric acid are uneconomical because the nitric acid must then be distilled and in some cases reconcentrated. It has now been found that 1-nitroanthraquinone sufficiently pure for the next stage of the process is obtained by using 90-72% nitric acid for the process of crystallisation and the purification associated with it, and by adjusting the mole fractions accordingly to values between .gamma..sub.HNO.sbsb.3 = 0.70 and .gamma..sub.HNO.sbsb.3 = 0.42.
The following possible combinations can be employed for stopping the reaction and for subsequent purification in the process according to the invention.
If the reaction is stopped by the addition of a small quantity of water and/or by distilling off nitric acid and/or by cooling the reaction mixture, the required mole fraction for precipitation of 1-nitroanthraquinone can be adjusted by adding water and/or dilute nitric acid and/or by distilling off nitric acid.
If a mole ratio of nitration products and unreacted anthraquinone to nitric acid of .ltoreq.12:1 is obtained by distilling off nitric acid, or if nitration is carried out with these mole ratios, then 1-nitroanthraquinone precipitated at temperatures of up to 15.degree. C can be separated from the by-products in the filtrate. These by-products can be precipitated almost completely from the filtrate if the mole fraction is adjusted to a value of .ltoreq.0.4, e.g., by dilution with water or by partial or complete removal of nitric acid by distillation. This precipitated mixture of by-products which is removed in the usual manner contains almost all the 2-nitroanthraquinone. This can be isolated in a relatively pure form by carrying out the aforesaid precipitation as a fractional precipitation. Nitric acid free from organic products can be returned to the process, for example after reconcentrating it, or as a diluent.
1-Nitroanthraquinone precipitated from nitric acid is obtained in a crystalline form and can be filtered off relatively easily (e.g. by means of a rotary, plane or pressure filter). The filter cake, after having been briefly washed with dilute nitric acid, may be washed until neutral with water in the usual manner and dried, or it may be directly freed from nitric acid in a vacuum (e.g., using a flow drier or roller drier). The dried 1-nitroanthraquinone is then subjected to vacuum distillation, in particular rectification.
The temperatures and pressures given below indicate the conditions at the head of the distillation apparatus.
Distillation may be carried out at a temperature of 200.degree.-400.degree. C and 0.5 to 100 Torr, preferably 235-330.degree. C and 1.5 to 50 Torr, in particular at 245.degree.-315.degree. C and 2.5 to 35 Torr. It has been found particularly suitable to carry out the distillation at temperatures of between 265.degree. and 300.degree. C and under a vacuum of 5 to 20 Torr. The whole process may be carried out continuously or discontinuously.
According to one particular variation, the already partly purified product and a solvent which boils at a temperature of 100.degree. to 350.degree. C, which is stable under the distillation conditions and which is inert towards the product, for example high boiling hydrocarbons or silicone oils, are distilled off together under the conditions indicated above, and in particular at 200.degree. to 350.degree. C and 0.5 to 100 Torr. 1-Nitroanthraquinone which crystallises from the condensate is then removed by conventional methods.
The process according to the invention may, for example, be carried out according to the following variations: